CN111617727A

CN111617727A - Electrical heating type reforming reactor and reforming hydrogen production system

Info

Publication number: CN111617727A
Application number: CN202010603815.4A
Authority: CN
Inventors: 余皎; 沈建跃; 孙荣江
Original assignee: Shanghai Palcan New Energy Technology Co ltd
Current assignee: Shanghai Palcan New Energy Technology Co ltd
Priority date: 2020-06-29
Filing date: 2020-06-29
Publication date: 2020-09-04

Abstract

The invention provides an electric heating type reforming reactor and a reforming hydrogen production system. The reactor body is internally provided with a plurality of gas channels and a plurality of electric heating part mounting positions. The catalyst carrier is filled in the gas channel; the catalyst carrier is made of metal wires, and the surfaces of the metal wires are attached with catalyst coatings. The electric heating part is installed at the electric heating part installation position. The invention has the beneficial effects that: the whole reforming hydrogen production system adopts a detachable structural design, the metal wire can be replaced during maintenance, and the metal wire with a catalyst failure can be detached for regeneration, so that the service life of equipment is prolonged. The whole system has the advantages of simple structure, convenient assembly and disassembly, low cost, long service life, safety and reliability.

Description

Electrical heating type reforming reactor and reforming hydrogen production system

Technical Field

The invention relates to a reforming hydrogen production system, in particular to an electric heating type reforming reactor using a metal wire cluster as a catalyst carrier, belonging to the technical field of methanol steam reforming hydrogen production.

Background

The methanol reforming hydrogen production uses a mixture of methanol and water as a raw material, is heated and evaporated into a gaseous state, and then is subjected to catalytic conversion in a reformer to obtain reformed gas. The reforming reaction is an endothermic reaction, is sensitive to temperature, and can be continuously, efficiently and stably carried out only by continuously keeping the raw materials and the catalyst in a proper temperature range. The temperature of the reformer is kept stable, the phenomenon that a local high-temperature area is generated to cause the inactivation of a reforming catalyst is prevented, heat is continuously and stably supplied to the reformer, and the method is a hotspot for researching a methanol reforming hydrogen production fuel cell.

In the existing methanol steam reforming hydrogen production system, the forms of a tubular reactor, a plate reactor, a microchannel reactor and the like all have or have the defects of low reaction efficiency, large pressure drop, short service life, inconvenience in replacement and the like. There is a need for a new reforming reactor that overcomes the above-mentioned disadvantages.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the existing reforming reactor has the disadvantages of low reaction efficiency, large pressure drop, short service life and inconvenient replacement.

In order to solve the above technical problem, a first aspect of the present invention provides an electrically heated reforming reactor, comprising:

the reactor comprises a reactor body, wherein a plurality of gas channels and a plurality of electric heating part mounting positions are arranged in the reactor body, the first ends of the gas channels are communicated with a reformed gas inlet of a reforming reactor, and the second ends of the gas channels are communicated with a reformed gas outlet of the reforming reactor;

the catalyst carrier is filled in the gas channel; the catalyst carrier is made of metal wires, and the surfaces of the metal wires are attached with catalyst coatings;

the first end cover is connected to the first end of the reactor body and provided with a reformed gas inlet;

the second end cover is connected to the second end of the reactor body and provided with a reformed gas outlet;

the electric heating part is installed at the electric heating part installation position.

In some embodiments, the first end cap is removably mounted to the first end of the reactor body and/or the second end cap is removably mounted to the second end of the reactor body.

In some embodiments, the first end cap is welded to the first end of the reactor body and the second end cap is flanged or clip-mounted to the second end of the reactor body.

In some embodiments, the first end cap has a cavity between the first end cap and the first end of the reactor body, and the reformate gas inlet is mounted radially of the first end cap.

In some embodiments, the second end cap is tapered, and the reformate gas outlet is disposed at the apex of the taper of the second end cap.

In some embodiments, the gas channels are straight channels, and each gas channel is packed with a plurality of catalyst carriers in a compact manner along the axial direction.

In some embodiments, the catalyst support is a cylindrical cluster made of iron-chromium-aluminum wires, and the porosity of the cylindrical cluster is 40% to 85%.

In some embodiments, each cylindrical cluster has a diameter of 15 to 30mm and a length of 15 to 30 mm.

In some embodiments, the number of cylindrical clusters filled in the gas channel is more than 20% to 50%.

In some embodiments, the iron-chromium-aluminum wire has a diameter of 0.01 to 3 mm.

In some embodiments, the catalyst coating is Pt-In/gamma-Al₂O₃Or Pd-ZnO/gamma-Al₂O₃The thickness of the catalyst coating on the surface of the iron-chromium-aluminum wire is 0.005-2 mm.

In some embodiments, a limiting part is arranged in the gas channel and used for limiting the sliding of the catalyst carrier, and the second end of the gas channel is provided with a wire mesh partition plate.

In some embodiments, the electric heating part is an electric heating rod, and a plurality of electric heating rods are arranged at intervals with a plurality of gas channels.

In a second aspect of the invention, an electrically heated reforming reaction hydrogen production system is provided, which comprises the electrically heated reforming reactor.

The invention has the beneficial effects that: the whole reforming hydrogen production system adopts a detachable structural design, the iron-chromium-aluminum wires can be replaced during maintenance, and the failed iron-chromium-aluminum wires can be detached for recycling, so that the service life of the equipment is prolonged. The whole system has the advantages of simple structure, convenient assembly and disassembly, low cost, long service life, safety and reliability.

Drawings

FIG. 1 is a working schematic diagram of the low-temperature electric pile working condition of the reforming reaction hydrogen production system.

FIG. 2 is a working schematic diagram of the high temperature stack operating mode of the reforming reaction hydrogen production system of the present invention.

FIG. 3 is a schematic view of the overall appearance of an electrically heated reforming reactor according to a preferred embodiment of the present invention.

FIG. 4 is a sectional view of a first view of an electrically heated reforming reactor in accordance with a preferred embodiment of the present invention.

FIG. 5 is a sectional view of a reforming reactor in an electrically heated form in a second preferred embodiment of the present invention.

FIG. 6 is a sectional view of a reforming reactor in a preferred embodiment of the present invention, taken from a third perspective.

FIG. 7 is a schematic diagram of the structure of an electrically heated reforming reactor (with the heating rods removed) in accordance with a preferred embodiment of the present invention.

FIG. 8 is a sectional view schematically showing the structure of an electrically heated reforming reactor (excluding heating rods) according to a preferred embodiment of the present invention.

The reference numerals in the above figures are as follows:

100 reactor body

110 gas channel

120 electric heating rod jack

130 mesh screen partition

140 body flange

200 first end cap

210 end cap wall

220 end cover plate

230 end cap pipe

240 reformed gas inlet

300 second end cap

310 reformed gas outlet

320 end cap flange

400 electric heating rod

410 heating part

420 wiring part

Detailed Description

Unless otherwise defined, technical or scientific terms used in the claims and the specification of this patent shall have the ordinary meaning as understood by those of ordinary skill in the art to which this patent belongs.

As used in this specification and the appended claims, the terms "first," "second," and the like do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a" or "an," and the like, do not denote a limitation of quantity, but rather denote the presence of at least one. In the description of this patent, unless otherwise indicated, "a plurality" means two or more. The word "comprising" or "having", and the like, means that the element or item appearing before "comprises" or "having" covers the element or item listed after "comprising" or "having" and its equivalent, but does not exclude other elements or items.

In the description of this patent, it is to be understood that the terms "upper," "lower," "left," "right," "horizontal," "lateral," "longitudinal," "top," "bottom," "inner," "outer," "clockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings to facilitate the description of the patent and to simplify the description, but are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the patent.

In this example, a cylindrical cluster body made of a catalyst-coated iron-chromium-aluminum wire was used, and the shape of the inner wall of a reaction tube (gas channel) in which a reforming reaction was performed was made to conform to the shape, and then the cluster body was inserted into the reforming reaction tube and tightly mounted. The front end of the gas channel is limited by adopting a welding spot structure, and the replaceable iron-chromium-aluminum wire column is limited by adopting a wire mesh partition plate at the rear end. A plurality of gas channels are connected in parallel for amplification, and the number of the gas channels can be adjusted according to actual required power. An electric heating rod is added between the gas channels for supplying heat to offset the heat absorption of the reforming hydrogen production reaction, so that the reforming reaction is continuously carried out at 340-380 ℃. The front end and the rear end of the gas channel are provided with limiting structures, and the number of the cylindrical clusters in the gas channel can be adjusted according to actual power and service life. The whole reforming hydrogen production system adopts a detachable structural design, adopts a flange connection structure at the rear end, can replace the iron-chromium-aluminum wire cylindrical cluster body during maintenance, and can be detached for regeneration and use when the cluster body with a catalytic effect failure is removed, so that the service life of equipment is prolonged. The whole system is simple in structure, convenient to disassemble and assemble, low in cost, long in service life, safe and reliable.

Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

FIG. 1 is a working schematic diagram of the low-temperature electric pile working condition of the reforming reaction hydrogen production system. FIG. 2 is a working schematic diagram of the high temperature stack operating mode of the reforming reaction hydrogen production system of the present invention. The mixture of methanol and steam (the optimal molar ratio of the methanol to the steam is 4: 6) is gasified by an evaporator and then enters a reformer for reforming reaction, and reformed gas generated by the reforming reaction enters a galvanic pile for generating electricity. The CO in the reformate gas can damage the catalyst of the low temperature stack and needs to be removed first by a "CO-preferential oxidizer," as shown in fig. 1. The CO has little influence on the catalyst of the high-temperature electric pile, and the device of 'CO preferential selective oxidizer' can be omitted, as shown in figure 2.

The core device of the reforming hydrogen production system is a reforming reactor. Fig. 3 discloses an electrically heated reforming reactor, which is mainly composed of a reactor body 100, a first end cap 200, a second end cap 300, and an electrical heating rod 400. The first end cap 200 is coupled to an axial first end of the reactor body 100, and the first end cap 200 is provided with a reformed gas inlet 240. The second end cap 300 is coupled to the second axial end of the reactor body 100, and the second end cap 300 is provided with a reformed gas outlet 310.

The reactor body 100 is provided with a plurality of gas channels and a plurality of electric heating rod inserting hole partition wall arrangements inside. As shown in fig. 6, 5 electric heating rod insertion holes 120 are arranged in a cross and divide the cross-section of the reactor body 100 into four regions, one of which is located each of the 4 gas passages 110. The arrangement can enable heat generated by the electric heating rods to reach the inside of the gas channel 110 in a short path, maintain the proper working temperature of the reforming reactor between 340 and 380 ℃, preferably 350 ℃, and realize accurate temperature control of the level by adopting the electric heating rods. The arrangement mode of the gas channel and the jacks of the electric heater can adopt other modes, and the heat transfer efficiency can be ensured.

As shown in fig. 4, the gas channel 110 has a cylindrical shape, and a catalyst carrier (not shown) is placed inside. The catalyst carrier adopts a cylindrical cluster body made of iron-chromium-aluminum wires, the outer surface profile of the cylindrical cluster body is consistent with the shape of the inner wall of the gas channel, and the cylindrical cluster body can be tightly and compactly arranged in the gas channel 110. The diameter of the iron-chromium-aluminum wire is 0.01-3 mm. Preferably, the diameter is 0.02-0.3 mm.

The surface of the Fe-Cr-Al wire is pre-coated with a catalyst, for example, including but not limited to Pt-In/gamma-Al₂O₃Or Pd-ZnO/gamma-Al₂O₃A catalyst. The thickness of the catalyst coating is 0.005-2 mm. Preferably, the thickness of the catalyst coating is 0.02-0.8 mm. The iron-chromium-aluminum wire is adopted because of high temperature resistance and low cost, and other metal wires with the same performance can be adopted to replace the iron-chromium-aluminum wire. In order to further enhance the catalytic efficiency, the inner wall of the gas channel 110 is coated with the same catalyst, and the thickness of the inner wall catalyst coating is 0.005-2 mm. Preferably, the thickness of the inner wall catalyst coating is 0.01-1 mm. More preferably, the thickness of the inner wall catalyst coating is 0.04-0.2 mm.

The surface and the interior of the cylindrical cluster body are porous, and the porosity is 40-85%. The preferred porosity is 60-75%. The sufficient pores are convenient for leading the reformed gas raw material to be fully contacted with the catalyst when passing through, and the catalytic reaction efficiency is improved.

Each gas channel 110 is filled with a plurality of the cylindrical clusters described above. The length of the single gas channel 110 is 15-30 cm. The diameter of each cylindrical cluster body is 15-30 mm, and the length of each cylindrical cluster body is 15-30 mm. Preferably, the cylindrical cluster has a diameter of 20mm and a length of 20 mm. A stopper (not shown) is provided in the gas passage 110. The limiting portion may be a protruding solder for hooking the cluster body and limiting the sliding of the cluster body in the gas channel 110. When the reformed gas passes from the inlet to the outlet of the gas passage 110, the gas pressure of the gas tends to cause the cluster body to slide forward. Therefore, no partition plate is required at the inlet of the gas channel 110 to allow the gas to more smoothly enter the gas channel 110, and a wire mesh partition plate 130 (or similar blocking member) must be provided at the outlet to block the cluster body from slipping out of the gas channel 110, as shown in fig. 5.

In a preferred embodiment, 9 fe-cr-al wire clusters are disposed in each gas channel 110. At the inlet of the gas channel 110, the degree of catalytic reaction is higher, where the catalyst on the surface of the fe-cr-al wire cluster takes part in the catalytic reaction sufficiently. The more to the rear end, the lower the extent of the catalytic reaction. Thus, the catalyst will be used to a different extent at different locations and will of course have different lifetimes. According to the experimental verification, for the newly used reforming reactor, the first 6 of 9 iron-chromium-aluminum wire clusters mainly participate in the reaction, when the gas reaches the 7 th and later clusters, the reforming reaction is almost finished, and the 7 th to 9 th iron-chromium-aluminum wire clusters are used as the standby ones. That is, the gas channel 110 is filled with the fe-cr-al wire cluster with a surplus of 50%. The suitable range of the surplus of the iron-chromium-aluminum wire cluster body is 20-50%. If the surplus is too small, the improvement on the operation life of the reforming reactor is limited; if the margin is too large, it is uneconomical.

With the long-term use of the reforming reactor, the catalyst of the 1 st fe-cr-al wire cluster will be completely ineffective, and at this time, the 2 nd to 7 th (or 6 total) fe-cr-al wire clusters participate in the catalytic reaction, and the 8 th and 9 th are still idle. When the 2 nd iron-chromium-aluminum wire cluster also fails, the 3 rd to 8 th (6 in total) iron-chromium-aluminum wire clusters participate in catalytic reaction, the 9 th iron-chromium-aluminum wire cluster is idle, and the rest is repeated, so that the design operation life of 2000-5000 h of the reforming reactor is ensured.

Both ends of the reactor body 100 are respectively connected with an end cover, so that in order to facilitate the replacement of the iron-chromium-aluminum wire cluster body, at least one part of the end covers at both ends is detachably connected. In a preferred embodiment, the first end cap 200 is welded and fixed to the first end (inlet end) of the reactor body 100 to ensure airtightness. The second end cap 300 is flange-mounted at the second end (outlet end) of the reactor body 100 for easy disassembly. The second end cap 300 is tapered and the reformed gas outlet 310 is provided at the apex of the taper, as shown in fig. 3, which facilitates the convergence of the gases. As shown in fig. 8, the bottom of the second end cap 300 extends outward to form an end cap flange 320, and the second end of the reactor body 100 also extends outward to form a body flange 140. End cap flange 320 and body flange 140 each have corresponding threaded holes and are secured by bolts. For positioning convenience, the front end of the body flange 140 is provided with a positioning structure matched with the inner wall of the second end cap 300. The second end cap may also be formed in other shapes, such as hemispherical, etc.

As shown in fig. 5, the first end cap 200 is integrally welded by the end cap wall 210, the end cap plate 220, and the end cap tube 230. The end cover plate 220 is provided with openings to which one end of the end cover tube 230 is connected and the other end of the end cover tube 230 is connected to an inlet of the electric heating rod insertion hole 120 of the reactor body 100. The electric heating rod 400 is inserted from the opening of the end cover plate 220, passes through the end cover tube 230 and finally is inserted to the bottom of the electric heating rod insertion hole 120. Each of the electric heating rods 400 is composed of a heat generating part 410 and a wire connecting part 420, as shown in fig. 3. The heat generating portion 410 is slightly exposed outside the end cap plate 220, so that the inside of the first end cap 200 is heated to maintain the temperature of the reformed gas raw material. Because of the space available in the end cap plate 220 due to the electrical heating rods, a reformate gas inlet 240 is provided in the end cap wall 210 of the first end cap 200 and radially into the cavity in the first end cap 200. Thus, the first end of the gas channel 110 communicates with the reformed gas inlet 240, and the second end of the gas channel 110 communicates with the reformed gas outlet 310.

Example 1

For the design of the 500W reforming reactor, 5 electric heating rods and 4 gas channels were used and arranged in an axial partition arrangement. The diameter of the electric heating rod is 10mm, and the length is 300 mm. The diameter of the electric heating rod insertion hole is 295mm, so that the front end of the electric heating rod is exposed by 5 mm.

The gas channel is an open pore structure and is a through hole with the diameter of 25mm and the length of 225 mm. The diameter of the entire reactor was 80 mm. The cavity section and the reaction section adopt a welding structure, and the reactor body and the first end cover (front end cover) adopt a welding structure. The reactor body and the second end cover (rear end cover) are connected by a flange, and the threaded holes are 6M 4. The outlet is a cone section with the length of 80 mm. The total length is about 380 mm. Both the inlet and outlet of the reformed gas were 4 minute tubes. The first end (front end) of the gas channel is evenly spot-welded with 3 welding spots for limiting, the second end (rear end) of the gas channel is limited by a screen mesh partition plate, and the smooth flow channel is ensured, and meanwhile, the inactivity of the iron-chromium-aluminum wire cylindrical cluster body is ensured and the gas channel can be detached. And axial and radial limiting is performed by using a cone angle. The cylindrical clusters are connected in series by 6 and 3 margins are added, 9 cylindrical clusters are arranged in each gas channel, and the total number of the cylindrical clusters in the whole reactor is 36. The diameter of the cylindrical cluster body is 20mm, the height length is 20mm, and the porosity is 70%. The wire diameter of the iron-chromium-aluminum wire is 1mm, and the thickness of the coated catalyst is 0.04 mm.

Compared with the prior art, the reforming hydrogen production system provided by the embodiment has the following characteristics:

(1) the catalyst using the iron-chromium-aluminum wire cluster as the carrier has reliability and also has considerable advantages in economy;

(2) the total surface area of the iron-chromium-aluminum wire cluster is large, the coverage rate of the catalyst is high, and the catalytic efficiency of hydrogen production reaction is high;

(3) the binding force of the catalyst coating and the iron-chromium-aluminum wire is high, and the catalyst coating is not easy to crack and fall off;

(4) the number of the gas channels can be adjusted according to the requirement;

(5) the number of the iron-chromium-aluminum wire clusters can be adjusted in the gas channel as required;

(6) the reforming reactor and the gas channel can be amplified in parallel according to the power requirement;

(7) the maintenance and the replacement are convenient, and the catalyst on the iron-chromium-aluminum wire cluster body can be detached for regeneration after losing efficacy.

The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.

Claims

1. An electrically heated reforming reactor, comprising:

a catalyst carrier filled in the gas channel; the catalyst carrier is made of metal wires, and a catalyst coating is attached to the surfaces of the metal wires;

a first end cap connected to a first end of the reactor body, the first end cap being provided with the reformed gas inlet;

a second end cap connected to a second end of the reactor body, the second end cap being provided with the reformed gas outlet;

an electric heating part installed at the electric heating part installation site.

2. An electrically heated reforming reactor as claimed in claim 1, wherein the first end cap is removably mounted to the first end of the reactor body and/or the second end cap is removably mounted to the second end of the reactor body.

3. An electrically heated reforming reactor as claimed in claim 2, wherein the first end cap is welded to the first end of the reactor body and the second end cap is flanged or clip-mounted to the second end of the reactor body.

4. An electrically heated reforming reactor as claimed in claim 3, wherein a cavity is provided between the first end cover and the first end of the reactor body, and the reformed gas inlet is arranged radially of the first end cover.

5. An electrically heated reforming reactor as claimed in claim 3, wherein the second end cap is tapered and the reformed gas outlet is provided at the apex of the second end cap.

6. An electrically heated reforming reactor as set forth in claim 2, wherein said gas passages are straight passages, and a plurality of said catalyst carriers are densely packed in each of said gas passages in the axial direction.

7. An electrically heated reforming reactor as claimed in claim 6, wherein the catalyst support comprises a cylindrical cluster made of fe-cr-al wires, and the porosity of the cylindrical cluster is 40-85%.

8. An electrically heated reforming reactor as claimed in claim 7, wherein each cylindrical cluster has a diameter of 15 to 30mm and a length of 15 to 30 mm.

9. An electrically heated reforming reactor as claimed in claim 7, wherein the gas passage is filled with the cylindrical cluster in an amount of 20 to 50% by weight.

10. An electrically heated reforming reactor as claimed in claim 7, wherein the diameter of the fe-cr-al wires is 0.01 to 3 mm.

11. An electrically heated reforming reactor as claimed In claim 7, wherein the catalyst coating is Pt-In/γ -Al₂O₃Or Pd-ZnO/gamma-Al₂O₃And the thickness of the catalyst coating on the surface of the iron-chromium-aluminum wire is 0.005-2 mm.

12. An electrically heated reforming reactor as set forth in claim 1, wherein a stopper is provided in said gas passage for restricting sliding movement of said catalyst carrier, and a wire mesh partition is provided at a second end of said gas passage.

13. An electrically heated reforming reactor as set forth in claim 1, wherein said electrical heating means comprises electrically heated rods, and a plurality of said electrically heated rods are arranged in spaced relation to a plurality of said gas passages.

14. An electrically heated reforming reaction hydrogen production system comprising the electrically heated reforming reactor according to any one of claims 1 to 13.